Method for the purification of organic polyisocyanates by fractional distillation in presence of an inert gas or superheated vapor of an organic solvent



Dec. 22, 1970 @SAMU ADlcA ET AL 3,549,504

l METHOD FOR THE PURIFICATION OF ORGANIC POLYISOCYANATES BY FRACTIONAL DISTILLATION IN PRESENCE OF AN INERT GAS Y OR SUPERHEATED VAPOR OF AN ORGANIC SOLVENT Filed May 5, 196'? 2 Sheets-Sheet l fn erf @s WSF 3m n. Sm Q', MR M N RQ t? RE n E E E m gw u), E n n i. "gm m E 'SS 3 ,um QJ n 2E i: @131 'ND Q KD a 1; Q8, Nb Q u 'N N f N'Q. B DQ .32 (AQ f Q N ENS Q NY b g d INVENTORS osAMu ADICA Q S KENJ: NAlTo o KATsUHlKo oGlNo fg HIRoY KURODA 3,1 BY i Q L@ 761ML ATTORNEYS Dec. 22, 1970 osAMU ADlcA ETAL l 3,549,504

METHOD FOR THE PURIFICATION OF' ORGANIC POLYISOCYANATES IIY FRACTIONAL DISTILLATION IN PRESENCE OF AN TNERT GAS OR SUPERHEATED VAPOR OF AN ORGANIC SOLVEN'I Filed May 5, 1967 ZSheets-Sheet 2 KATSUHIKO OGINO 4 HIROY Kl KURODA BYZA t ffarlj? ATT( )R N l "YS United States Patent O METHOD FOR THE PURIFICATION OF ORGANIC POLYISOCYANATES BY FRACTIONAL DISTIL- LA'I'ION IN PRESENCE OF AN INERT GAS OR SUPERHEATED VAPOR OF AN ORGANIC SOLVENT Osamu Adica and Kenji Nato, Toyonaka, Katsuhiko Ogino, Minoo, and Hiroyuki Kuroda, Suita, Japan, assignors to Takeda Chemical Industries, Ltd., Osaka,

Japan Filed May 5, 1967, Ser. No. 636,353 Claims priority, application Japan, May 5, 1966, 41/ 28,431; May 10, 1966, 41/29,842 Int. Cl. B01d 3/34; C07c 69/00 U.S. Cl. 203-49 15 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a method for the purification of crude organic polyisocyanates.

More specifically the invention relates to a method for purification of crude organic polyisocyanates by subjecting it to a fractionation under specifically defined conditions, whereby light or residual impurities are cut.

An organic polyisocyanate, when produced by reacting the corresponding amine with phosgene, inevitably contains various by-products having relatively low boiling points. This makes it necessary to submit the product mixture to a further purification process. Organic polyisocyanates, as is well known, have relatively high boiling points and are very unstable when heated. Heretofore, for the purpose of purifying the materials having high boiling point and which are susceptible to deterioration upon heating, a vacuum distillation method has usually been employed. However, in this method, the material to be purified is eventually subjected to a comparatively high temperature due to a remarkable rising of temperature necessarily caused around the bottom of distillation column by pressure drop. Therefore, organic polyisocyanates can not be safely purified by this method.

To solve this problem, various attempts to minimize the pressure drop in the distillation column have been made. For example, there has been the employment of various types of trays such as Ballast tray, Ripple tray, Venturi Caskade tray, or improvement or developments of the various materials to be packed in the column such as MacMahon. However, control of pressure drop cannot be satisfactorily attained by these means.

Recently, vacuum fractionating apparatus such as Spinning Band Still, Brush Still, Rotary Column and Luwa fractionator or falling film type fractionation column have been developed for the purpose of attaining effective control of the pressure drop. But these apparatuses also have not given satisfactory results since the mechanically complicated design of such apparatuses are not suitable for fractionation on a commercial scale.

The present invention is based upon the discovery that purification by fractionation of crude organic polyisocyanates can easily be effected at a low temperature with ice a conventional fractionation column such as tray column or packed column by selecting specific fractionation conditions.

The present method comprises subjecting the crude organic polyisocyanate including light impurities to fractionation by allowing the crude organic polyisocyanate to contact an inert gas in a fractionation column under such conditions that the pressure at the top of the fractionation column is lower than 200 mm. Hg, and the feed rate (C) of inert gas is ranges from 0.05 to 0.50, the value of Ev ranges 0.3 to 1.0 and the value of gli ranges from 0.2 to 20.

wherein the value of and wherein Pzoperating pressure at the bottom of column (mm. Hg).

Px=equilibrium vapor pressure of residue at bottom of column at the operating temperature.

Xpzmolar concentration of light components in refiux fluid (mol fraction).

Xf=molar concentration of light components in crude organic polyisocyanate (mol fraction).

Yf=molar concentration of light components contained in equilibrium vapor of crude organic polyisocyanate in feed tray at the operating temperature (mol fraction).

F=feed rate of crude organic polyisocyanate (mol/hr).

W=transfer rate of residue (mol/ hr) Xwzmolar concentration of light components in residue (mol fraction).

:parameter determined by properties of a crude organic polyisocyanate and construction of the fractionation apparatus.

Evzvaporization efficiency.

FIG. l is a flow sheet of the invention illustrating the purification of polyisocyanate using an inert gas; and

FIG. 2 is a fiow sheet of the invention wherein a superheated vapor of an organic solvent is used in the purification of polyisocyanates.

According to the present invention, a pressure drop at the bottom of the fractionation column can effectively be improved. Therefore, by this invention crude organic polyisocyanate can easily and sufficiently be purified by fractionation using simple apparatus such as tray column and packed column accompanied by no degradation of polyisocyanate due to heating.

The object of the present invention is to provide a novel method for purification by a fractionation of crude organic polyisocyanate containing light impurities.

Another object of the invention is to provide pure organic polyisocyanate subtautially free from light impurities from corresponding crude organic polyisocyanate in a high yield by a simple procedure using a simple and available apparatus.

The organic polyisocyanates to be treated by the present method, are exemplified by crude xylylenediisocyanate (XDI,

NC O-CHz CHzNC O meta, para, ortho or mixtures thereof), hexamethylenediisocyanate, 4,4'diphenylmethane diisocyanate, tolylenediisocyanate (2,4-isomer, 2,6-isomer, or mixtures thereof), toluene-2,4,-trisocyanate. Such polyisocyanates are obtained by phosgenation of the corresponding diamines in the conventional manner.

The crude organic polyisocyanates may be treated by the present method in the form of the phosgenation products Without any preparatory treatment. However, it is desirable that before being treated by the present method, the crude organic polyisocyanates be subjected to a simple distillation in a conventional manner so as to remove high-boiling constituents therefrom.

As inert gases, there are used, for example, nitrogen gas, air, natural gas, carbon dioxide gas and an inert gas mainly consisting of nitrogen, which is obtained by combustion of hydrocarbon. There can also be employed any other gases so long as they are inert with respect to, i.e. do not react with, the organic polyisocyanate.

-In the present method, either batch-wise or continuous process may be employed, though the later is desirable, and any conventional fractionating apparatus may be used. Such apparatus is exemplified by tray column, such as Bubble cap tray column, Sieve tray column, Ballast tray column, Ripple tray column, Iet tray column; or packed column packed with MacMahon, Pall4 ring and Raschig ring, etc.

The following description is limited to the aspect where light component is cut as impurity. However, as a matter of course, the following method may be applied to the case wherein high-boiling constituent is cut as impurity.

In the method of the present invention the crude organic polyisocyanate to be purified and inert gas are introduced into a fractionation column and allowed to intimately contact with each other under conditions of heating. The pressure at the top of the fractionation column and the feed rate of the inert gas are specifically determined. First of all, the pressure at the top of the fractionation column is selected from a range of about 5 to about 200 mm. Hg, more preferably, 20 to 150 mm. Hg. And the feed rate of the inert gas is determined by the above Equations I to III in the following manner.

First, the composition of the organic polyisocyanate to be purified is determined. When the organic polyisocyanate is determined, operating temperature may be suitably determined in accordance with the stability to heating of the particular organic polyisocyanate. Generally, this temperature will be selected in the range of 90 to 220 C. For example, when crude TDI is purified, the temperature may be from 100 t0 190 C.; when crude XDI is used the range may be from 100 to 170 C.; and when crude MDI is used it may be from 100 to 210 C.

The amount and the desired purity of the purified organic polyisocyanate are suitably determined in respective cases. Generally, the desired purity will range from 98 to 100%.

The Value of PB as mentioned above is determined within a range of about 5 to about 200 mm. Hg, more preferably 50 to 200 mm. Hg.

The value of F is determined in accordance with the necessary amount of purified organic polyisocyanate,

The value of PX is calculated from the purity of desired organic polyisocyanate and operating temperature, since the purified organic polyisocyanate obtainable by the present method substantially corresponds to volatile components of the mixture accumulated at the bottom of the column.

The value of Xp is previously hypothetically determined taking into account the type of fractionation column, etc., and after a trial with the use of this hypothetical value is carried out, any necessary correction is made. The value of Xp is a molar fraction of impurities to be cut from the top of the column, which are contained in the reflux fluid, and it is desirable to make the value as high as possible. Generally, the value of XD ranges from 0.4 to 0.9.

The value of Xf can be found by an analysis of molar concentration of impurities contained in the Icrude organic polyisocyanate to be purified.

The value of Yf is determined from vapor-liquid equilibrium data of a two-component system consisting of impurity and organic polyisocyanate.

As the residue is the purified organic polyisocyanate, the value of W shows a transfer rate of purified organic polyisocyanate recovered from the bottom of the column.

The value of XW shows molar concentration of impurities in purified organic polyisocyanate and can be determined from the purity of desired organic polyisocyanate.

The values of and Ev are suitably determined within a range of about 0.2 to about 20 and about 0.3 to about 1.0, respectively.

Further, the value of PmEv/PB is controlled within a range of about 0.05 to about 0.50 by suitably selecting the value of PB within the range of 5 to 200 mm. Hg.

By the use of the thus-determined values, the value of C which is the feed rate of inert gas is calculated from EquationI o= m P together with the Equations II and III.

Necessary correction of the value kof C so calculated may be effected after one or more trials with the use of the calculated value.

In this manner the value of C actually applicable is finally determined.

The fractionation of the present method is conducted under thus determined operation conditions.

For controlling the operating conditions (i.e. pressure at the bottom of the column, feed rate of inert gas, etc.) to previously determined values, any conventional means may be applied. Such means are known in the art.

Further for a better understanding of this invention, the operation process of the present method is explained referring to the drawing.

FIG. 1 is an example of a flow sheet of the continuous apparatus employable in the present method. In FIG. 1, crude organic polyisocyanate (hereinafter referred to as PI) is led to Fractionation Column (C) through Preheater (D). An inert .gas (hereinafter referred to as IG) being heated in Heater (A) is led to Reboiler (B) from Gas-Tank (L) and then to Fractionation Column (C) and flows upward with vapor of PI and impurities, in the Fractionation Column (C). In Fractionation Column (C), crude PI is separated into light impurities and pure PI. Thus-separated light impurities are concentrated at the top of the column, and then condensed at Total Condenser (E), while pure PI is led to Reboiler (B). A part of the condensate in Total Condenser (E) is returned to the Fractionation Column (C) as refiux fluid and the other is drawn olf as Distillate (DL). The inert gas not condensed in Total Condenser (E), is sucked by Vacuum Pump (I) through Purification Column (F) and (G) and Vacuum Tank (H), and is collected in Vacuum Tank (M) and then returned to the Gas Tank (L) through Blower (N) and Purification Column (I) and (K). Purified PI is drawn off as Residue (BL) from Reboiler (B).

In the following examples of the present invention, parts is by weight, unless otherwise stated.

EXAMPLE 1 200 parts of phosgene dissolved in 200 parts of o-dichlorobenzene at -5 C. is mixed With 68 parts of a mixture of 30 parts of p-xylenediamine and 701 parts of m-xylenediamine dissolved in 400 parts of o-dichlorobenzene. The mixture is gradually heated to 170 C. for 2 hours while introducing an excess amount of phosgene to allow a reaction to take place. After the reaction, nitrogen gas is introduced into the resultant mixture to remove the excess phosgene. Then the solvent is distilled off from the treated resultant mixture to give a crude mixture of p-xylenediisocyanate and m-xylylenediisocyanate (referred to as XDI), which includes 3.5 parts of impurities and high-boiler. The crude XDI is subjected to simple distillation under a condition of 13S-140 C./3 mm. Hg to cut the high-boiler.

Thus treated crude XDI is fractionated utilizing a system as described in FIG. 1 and using nitrogen as inert gas.

The type of each of the apparatuses used is as follows:

Fractionation Column: glass column packed with stainless steel;

MacMahon (length: 2000 mm., inner diameter: 50 mm.);

Preheater: falling lm type heater;

Reboiler: Iacketed vessel with gas feed ring (capacity about 2 liters);

Heater: Plate n type heater;

Partial Condenser: shell and tube type;

Total Condenser: shell and tube type.

As inert gas, nitrogen gas is used.

The feed rate of nitrogen gas is determined as follows:

First, the operating temperature, that is to say, the temperature of the bottom of the column is adjusted to about 160 C. This temperature is used since m-XDI iS caused to be polymerized by heating at a temperature higher than 170 C. The feed rate of crude XDI, F, is determined at a rate of 1100 parts per hour. The operating pressure at the top of the column is determined as 30 mm. Hg taking into acount the construction of the column.

Considering thus determined operating pressure at the top and pressure drop occurring in the column, the pressure at the bottom of the column PB is estimated as about 45 mm. Hg. The purity of desired XDI is determined as 99.8%. From the purity of desired XDI and the operating temperature, the value of PX is calculated as mm. Hg. The value of Xp is tentatively determined as 0.80. The value of Xf is found to be 0.02. The value of W is approximately equal to the value of F since the value of W represents the transfer rate of purified organic polyisocyanate as previously described. In the calculation, the value of XW can be taken as being 0. The value of EV is 0.60. The value of Yf is determined as 0.05. From thus determined value, R is calculated by the Equation II;

P is calculated by the Equation III;

P=0.147 mol./hr.

and, C is calculated by the Equation I;

=395 parts by volume/hr.

wherein 1.38 is a parameter experimentally determined depending upon properties of crude XDI and the structure of the column. Thus, the feed rate of nitrogen gas actually applied is determined as about 400 parts by volume per hour. The values obtained in the calculations are utilized in the operation within a tolerance of 10% Actual operation is carried out by applying thus obtained values as follows:

The crude XDI is heated in the preheater at 155 C. and is fed into the column from the middle part thereof at a rate of 1000 parts/hr. The nitrogen gas is heated in X 1.38= 17.8 mol/hr.

preheater at 160 C. and is blown into the reboiler at a rate of 400 parts by volume/hr. at normal pressure and temperature. The column is maintained at an operating pressure of 30 mm. Hg at the top. The temperature of reboiler is set at 162 C. The temperature at the top XDI (weight percent) t Impurities (weight percent) Residue 99.94 0.06 Distillate 28.8 71.2

Impurities mainly consisting of chloromethyl benzyl isocyanate.

Thus produced residue is subjected to a simple distillation under conditions of -170" C./1 mm. Hg to give purified XDI of a purity of 99.9% in a yield of 93 parts relative to crude XDI charged.

EXAMPLE 2 The fractionation of crude diphenylmethane-4,4diisocyanate (referred to as 4,4MDI) is carried out by the use of the same apparatus as in Example 1.

4,4 MDI is produced by phosgenating diphenylmethane-4,4diamine (referred to as 4,4-MDA). This crude MDI includes about 2 parts of impurities per 100 parts of crude MDI (mainly consisting of diphenylrnethane-2,4diamine) As the inert gas, nitrogen gas is used. Nitrogen gas feed rate is determined in the same manner as in Example 1.

Actual operation is carried out as follows:

4,4-MDI (2,4-MDI content 2 parts) maintained at 60 C. is fed into a preheater to be preheated to 195 C., and is led to a preheated fractionation column from the middle part thereof at a rate of I600 parts per hour. Nitrogen gas having been preheated to 250 C. in a preheater is led to the fractionation column through a Reboiler at normal pressure and temperature at a rate of 350 parts by volume/hr. The column is maintained at an operating pressure of 20 mm. Hg at the top. The temperature of the column is maintained at 172 C. at the top after a stationary state is attained. The reux ratio is 5.0. The fractionation is carried out continuously for 15 hours during which period 500-530 parts per hour of the residue is continuously taken out from the reboiler.

After a stationary state is attained, distillate and residue are analyzed by gas chromatography, the result of which is as follows:

wt. percent Residue 0.3 Distillate 60 The thus produced residue is subjected to a simple distillation under conditions of ISO-190 C./0.5-1 mm. Hg to give purified 4,4-MDI of purity of 99.7% in a yield of 94% (w./W.) relative to crude MDI charged.

EXAMPLE 3 Crude XDI produced by the same procedure as in Example l is fractionated as follows:

The apparatus is the same as in Example 1. As inert gas, propane gas is used. The propane gas (purity: higher than 98%) feed rate is determined by the same manner as in Example l. The crude XDI (Impurities content: 2%) is preheated at C. in a preheater and is led to the fractionation column from the middle part of column at a rate of 9000 parts/hr. The propane gas is heated in the preheater to C. and blown into fractionation column at normal pressure and temperature at the rate of 658 parts by volume/ hr.

Weight percent XDI Impurities* Residue 99. 8 n. 2 Distillate 15. 85. 0

*Impurities consisting mainly of chlorometliyl benzyl isoeyanate. The simple distillation of the residue gives purified XDI of a purity of 99.7% in a yield of 94% ('w./w.) relative to crude XDI charged.

EXAMPLE 4 Hexamethylene diisocyanate (HMDI) is produced by phosgenating hexamethylene diamine. The thus prepared crude HMDI includes about 6% of impurities (mainly 1-chloro--isocyanatohexane). The boiling point of the impurities is slightly lower than that (127 C./ 10 mm. Hg) of HMDI.

Thus prepared crude HMDI is fractionated by the use of the same apparatus as in Example 1. As inert gas, nitrogen gas is used. Nitrogen gas feed rate is determined by the same manner as in Example 1. The crude HMDI is heated to 145 C. in a preheater and supplied to the fractionation column from the central part at a rate of 750 parts per hour. Nitrogen gas is heated to 150 C. in a preheater and blown into a fractionation column at a rate of 295 parts by volume per hour.

The operating pressure is 50 mm. Hg at the top of the column. The operating temperature is set at 150 C. in the Reboiler, whereby the temperature at the top of the column is maintained at 130 C. The reflux ratio is 10.0. The fractionation is carried out continuously for 20 hours during which period 500-530 parts per hour of the residue are continuously taken out from the reboiler.

Analysis by gas chromatography of distillate and residue at a stationary state of the system is as follows:

The simple distillation of the residue gives purified HMDI of purity of 99.5% in a yield of 91% (w./w.) relative to crude HMDI charged.

EXAMPLE Tolylenediamine is phosgenated in the presence of odichlorobenzene. After the reaction, o-dichlorobenzene is distilled off to give tolylenediisocyanate (TDI) consisting of 80 parts of 2,4-tolylenediisocyanate and 20 parts of 2,6-tolylenediisocyanate. Thus prepared crude TDI includes o-dichlorobenzene, light impurities such as phenyldiisocyanate and tolylisocyanate and other unknown components. Content of the light impurities is about 3 parts relative to TDI and that of unknown impurities about 18 parts. The crude TDI is submitted to batch-wise fractionation to cut light impurities and to cut high-boiler as distillation residue.

Thus treated TDI is fractionated in a stainless steel sieve tray column having 20 trays (length 2.2 mm., inner diameter 180 mm.), at the bottom of which a Reboiler having Jacket (capacity 40 L) is equipped. As the inert gas, carbon dioxide is employed. Feed rate of carbon dioxide is determined by the same manner as in Example l. Into Reboiler, parts of the above mentioned crude TDI is charged. Carbon dioxide is blown into Reboiler at a rate of 6.3 parts by volume per hour. The pressure is controlled to 40 mm. Hg at the top of Column and temperature of Reboiler is controlled to C. The fractionation is, at first, carried out under total reflux until the temperature of the top of column becomes constant, and is then carried out under reflux ratio of 10:1 to cut light impurities. After the light impurities are also completely distilled off, pure TDI begins to distill out from the top of the column accompanied with a gradual rising of temperature at the top. Soon after the distillation of TDI begins, the reflux ratio is gradually lowered to about 1:1, under which conditions the distillation is further continued. When the distillation of TDI is almost complete-d, the reflux ratio is raised to about 4:1 to avoid a distillation of residue.

The distillation mentioned as above for totally 16 hours gives 21 parts of TDI (purity: 99.9%).

EXAMPLE 6 Toluene-2,4,6-triisocyanate (referred to as TTI) is produced by phosgenating 2,4,6-triaminotoluene in the presence of o-dichlorobenzene. This crude TTI includes some light impurities and high-boiler impurities. TI'I has a high boiling point and is susceptible to heating. The fractionation is carried out after similar manner to Example 5. As the inert gas, nitrogen gas is used. The apparatus ernployed is a glass column (800 mm. height) packed with M1 inch MacMahon up to a height of 750 mm. at the upper part of which is equipped a reflux controller. 30() parts of crude TTI are fed into the column and heated at C. The operating pressure is 30 mm. Hg at the top of the column. The nitrogen gas is blown at a rate of 100 parts by volume per hour. Hot water at 65 C. is circulated in the reflux condenser. The reflux ratio is adjusted to about 10:1. Under these conditions the fractionation is carried out, while a part of distillate is taken out to be analyzed by gas chromatography. After the amount of impurities contained in the distillate is found to be lowered, distillate is taken out of the system as purified 'ITI while gradually lowering the reflux ratio to about 1:1. Thus 65 parts of purified TTI (purity: 99%) are obtained.

In a further and particularly important aspect, this invention relates to a method for the purification of crude xylylenediisocyanate (hereinafter referred to as XDI).

More specifically, this aspect of the invention relates to a method for purification of crude XDI by subjecting to fractionation under specification conditions.

XDI has a formula of O CNCHz CHeNC O and is generally produced by reacting the corresponding Xylylenediamine with phosgene. Since various by-products, such as chlorine compounds represented by the following Formulae I to III (hereinafter referred to as impurity (I), (II) and (III) CHgCl (IHzCl CH3 CHzNCO CHzCl CHZNCO (I) (II) (IH) are produced in this reaction, the thus obtained crude XDI must be submitted t0 a process of purification.

XDI is well known in the art and is useful as a chain extender in the production of polyurethane foams, a well known and commercially valuable polymeric material.

XDI, as is well known, has a high boiling point (161 C. at 10 mm. Hg) and is so unstable to heating that it is polymerized by heating to temperatures higher than 170 C. The boiling points of the above-mentioned impurities are very near to that of XDI and moreover, the boiling point of impurity (I) which is produced in a greater amount than any other impurities, is closest to that of XDI.

In purifying the crude XDI, therefore, the most important problem to be solved is how to eliminate effectively the impurities (I) to (III), and especially impurity (I).

Heretofore, for the purpose of removing these impurities, a vacuum distillation method has been applied. In this method, however, the objective compound to be purified is eventually subjected to a comparatively high temperature since a remarkable raising of temperature due to pressure drop inevitably occurs near the bottom of a distillation column. In other words, in this method, the employment of a fractionation column having several trays is Irequired because of the little difference in boiling points between the impurities and XDI. Incidentally, the pressure drop amounts to considerable mm. Hg near the bottom of the column, whereby XDI is subjected to heating at about 180-200 C.

Therefore, by this method, XDI cannot satisfactorily be purified. For the purpose of solving this problem, many attempts to minimize the pressure drop in distillation column have been made. However, none of them has satisfactorily solved the problem.

The present invention is based on the disclosure that purification of crude XDI by fractionation can easily be completed without any bad effect on XDI itself at a low temperature with the use of hitherto-employed fractionation column such as tray column and packed column by selecting specific fractionation conditions,

'Ihe present method has been perfected on the basis of this discovery, and comprises subjecting crude XDI to fractionation by allowing the crude XDI to contact in a fractionation column with the superheated vapor of an organic solvent having a boiling point of from 20 C. to 150 C. at a pressure of 200 mm. Hg. 'Ihe` organic solvent is exemplified by aliphatic hydrocarbon having 2 to 11 carbon atoms, alicyclic hydrocarbon having 5 to 8 carbon atoms, aromatic hydrocarbon, halogenated aliphatic hydrocarbon having 1 to 6 carbon atoms, or halogenated benzene. The crude XDI and solvent vapor are contacted under such conditions that the pressure at the top of the column is maintained at to 200 mrn. Hg and the temperature at the bottom of the column is maintained at not higher than 170 C.

According to this aspect of the present invention, the pressure drop at the bottom of fractionation column can effectively be improved, and therefore crude XDI can easily and satisfactorily be purified by fraction with the use of simple apparatus such as tray column and packed column, accompanied with no degradation of XDI itself due to the heating.

The object of the aspect of the present invention is to provide a novel method for purification by fractionation of crude XDI including impurities having boiling points extremely close to that of XDI, that is to say, to provide a novel method for eliminating these impurities as light cuts from the crude XDI.

Another object of this aspect of the invention is to provide pure XDI substantially free from impurities in a high yield by simple procedure.

In this aspect of the present invention, XDI means not only o, m, or p-isomer but also any of the mixtures thereof.

This aspect of the present method can thus be applied to a purification of any of the isomers of XDI in a crude 10 state, i.e. to a purification of crude o-xylylenediisocyanate, m-xylylenediisocyanate, p-xylylenediisocyanate and mixtures thereof.

The XDI is generally obtained by phosgenation of the corresponding xylylenediamine and the phosgenation product as it is may be treated by the present method. However, it is desirable that before being treated by the present method, the crude XDI is subjected to a simple distillation by a conventional manner so as to remove high-boiler therefrom. Thus the removal of high-boilers is desirable but not essential.

As fractionation column, any conventional apparatus may be used in this method, which is exemplified by tray column such as Bubble cap tray column, Ballast tray column, Ripple tray column, Ict tray column or packed column packed with MacMahon, Pall ring, Raschig ring, and

so on.

As organic solvents, there may preferably be employed those which are stable and are inert with respect to XDI as Well as stable to heating and which also have a boiling point of 20 C. to 150 C. at a pressure of 200 mm. Hg more preferably 30 C. to 80 C. at a pressure of 200 mm. Hg. These are exemplified by aliphatic hydrocarbons having 2 to ll carbon atoms (eg. pentane, hexane, heptane, octane, nonane, decane, undecane, ligroin, etc.), alicyclic hydrocarbon having 5 to 8 carbon atoms (e.g. cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, etc.), aromatic hydrocarbon (e.g. benzene, secondary amyl benzene, toluene, ethylbenzene, xylene, etc.), halogenated aliphatic hydrocarbons having l to 6 carbon atoms (e.g. chloroform, dichloromethane, 1,2-dichloroethylene, nmonochlorobutane, carbon tetrachloride, n-monochloroheptane, n-monochlorohexane, 1,2-dichloroethane, tetrachloroethane, etc.) or halogenated benzene (eg. monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene. 1,4-dichlorobenzene, etc.

Of the above-mentioned solvents, there may be most preferably used such solvents as cyclohexane, benzene, toluene and xylene.

In this aspect of the present method, superheated gas of the above-mentioned organic solvent or mixture is contacted with crude XDI intercurrently in the fractionation column.

Practically, the superheated gas is produced in a preheater by heating the organic solvent at a temperature less than operating temperature of the fractionation column and supplying it to a reboiler.

The above-mentioned contact in the fractionation column is carried out under such conditions that the temperature at the bottom of the column is not higher than 170 C., the lower limit being around C. and a pressure at the top of the column is from 5 to 20() mm. Hg, more preferably 30 to 100 mm. Hg.

The operating pressure is preferably adjusted by automatic control device fixed in the fractionation system, and the operating temperature iseffectively adjusted by automatic control device fixed in a reboiler. The automatic control means for this pressure and temperature control are per se known.

In the method, either batch-wise or continuous process may be employed, though the latter is desirable.

For preventing from polymerization of XDI, the fractionation is carried out in the presence of a conventional polymerization-inhibitor if necessary.

For better understanding of this aspect of the invention,

eference is now made to accompanying drawings.

In FIG. 2, crude XDI (C-XDI) is led to fractionation column (B) through preheater (E). The superheated vapor of organic solvent, which is prepared by heating the solvent (S) in a heater (F), is led to reboiler (A) and then to fractionation column accompanying XDI vapor existing in reboiler (A). Superheated vapor of solvent flows upward with XDI vapor in the fractionation column (B). In fractionation column (B), crude XDI is separated into light impurities and pure XDI. Thus separated light impurities are concentrated at the top of column, while pure XDI is led to reboiler (A). The concentrated light impurities are led to the partial condenser (C) through the top of the column together with superheated vapor. The temperature of the partial condenser (C) must be Set so as to condense only the light impurities in it. A part of the condensed light impurities is reuxed and the other collected in a distillate receiver (I). The solvent vapor separated in the partial condenser (C) is led to the total condenser (D), wherein it is collected and used repeatedly. In FIG. 2, (V) represents a vacuum source and (J) represents a solvent receiver. On the other hand, XDI collected in reboiler (A) is led to a distillation apparatus (G) to be subjected to distillation, and then thus distilled XDI is led to the condenser (H) wherein XDI is condensed. Thus pure XDI (P-XDI) is collected from the condenser (H).

In the following examples of the present invention, parts is shown by weight, unless otherwise stated.

EXAMPLE A 200 parts of phosgene dissolved into 200 parts of o-dichlorobenzene at -5 C. is mixed with 68 parts of a mixture of 70 parts of m-xylenediamine and 30 parts of pxylenediamine dissolved in 400 parts of o-dichlorobenzene. The mixture is gradually heated to 170 C. for 2 hours while introducing an excess amount of phosgene to allow the reaction to take place. After the reaction, nitrogen gas is introduced into the resultant mixture to remove the excess phosgene. Then the solvent is distilled off from the thus treated resultant mixture to give crude XDI, which includes 3.5 parts of impurities and high-boiler. The crude XDI is subjected to a simple distillation under the conditions of 13S-140 C./ 3 mm. Hg to remove the high-boiler.

Thus treated crude XDI is fractionated following the system described in FIG. 2.

The type of the used apparatus is as follows:

Fractonation Column (B): Sieve tray column having 40 trays (inner diameter: 180 mm., height: 4.4 m.);

Preheater (E): Falling ilm type;

Reboiler (A): Jacketed vessel with gas feed ring;

Heater (F): Plate lin type heater;

Partial Condenser (C) Shell and tube type;

Total Condenser (D): Shell and tube type.

Ligroin is used as solvent. Ligroin is heated in heater up to 160 C. and led to a fractionation column through reboiler at a rate of 30400 parts per hour. The crude XDI is heated at 160 C. in preheater and led to fractionation column at a rate of 10000 parts per hour. The operating temperature is set by adjusting a temperature in the reboiler at 160 C. and the operating pressure is set by adjusting the pressure at the top of the column to 80 mm. Hg. The crude XDI is intercurrently contacted with the superheated gas of the solvent in the fractionation column. lmpurities and the superheated gas are led to partial condenser through the top of the column, wherein only impurities are condensed, while the superheated gas is condensed in the total condenser and collected. The abovementioned procedure is continuously conducted.

After about 20 hours, the fractionation system (reflux ratio, about 9.0) assumes a stationary state. XDI collected in reboiler is continuously led to the distillation apparatus at a rate of 9000 to 10000 parts per hour, wherein the XDI is subjected to distillation under conditions of 140 C./2-3 mm. Hg to yield puried XDI in a yield of 95 weight percent of crude XDI fed to fractionation column.

The analysis of thus obtained pure XDI is as follows:

Weight percent XD-I 99.5 Hydrolyzable chlorine 0.01 Toluene insolubles 0.02

After the stationary state is attained, the composition of the mixture in Reboiler (A) and that of the top of l2' the Fractionation Column (B) are also analyzed to obtain the following result:

1 Referred to as impurity (l).

EXAMPLE B Crude XDI produced by the same procedure as in Example A is purified as follows:

The type of apparatus used is the same as in Example A except that a glass column (height: 2000 mm., inner diameter: 50 mm.) packed with MacMahon made of stainless steel in place of the sieve tray column is used. As solvent, heptane is used. Heptane is heated in the heater at a temperature of C. and led to fractionation column through the reboiler at a rate of 200 parts per hour. The operating temperature is set at 160 C. at the reboiler. The crude XDI (impurity (I) content about 2%) is heated at 160 C. in the preheater and led to the middle point of the fractionation column at a rate of 500 parts per hour. The operating temperature is set by adjusting the temperature in the reboiler to 160 C. and the operating pressure is set by adjusting the pressure at the top of the column to 30 mm. Hg. Intercurrent contact of the crude XDI with superheated heptane gas in the column is continuously continued for several hours at a reflux ratio of 7.0 and under such temperature and pressure as mentioned above.

Then puried XDI is obtained in a yield of 94 weight percent of the crude XDI fed to column after a similar manner to Example A.

The analysis of thus obtained pure XDI is as follows:

Weight percent XDI 99.5 Hydrolyzable chlorine 0.02 Toluene insolubles 0.02

In the above procedure, after the stationary state is reached, the composition of the reboiler and that of the top of the fractionation column are also analyzed to obtain the following result:

1 Referred to as impurity (I).

EXAMPLE C A purification of Crude XD'I is conducted in a batchwise by the use of the following apparatus:

A glass column (inner diameter: 25 mm., height: 700 mm.) packed with 1A inch stainless MacMahon being vertically connected with 500 ml. flask which is equipped with inlet of crude XDI and that of superheated gas; the top of the glass column being jointed to partial condenser and total condenser in this order; and the inlet of superheated gas being connected -with another flask for vaporizing solvent.

Into the 500 ml. flask, 500 parts of crude XDI containing about 2 parts of impurity (I) is charged. The fractionation is carried out under such conditions as operating pressure being 30 mm. Hg at the top of the column and the operating temperature being C. at the bottom of the column and with blowing superheated vapor of xylene into the 500 ml. flask at a rate of 0.68 mole per hour through apipe from the flask for vaporizing solvent. PX W X During the fractionation, the xylene is thoroughly conf X "'(m01/hr IH densed at the total condenser cooled at 20 C., and D XDI condensed at the parti-al condenser is refluxed wherein thoroughly. After five hours, the sample is collected at P t. t th b tt f 1 the same time from the top of column and ask. Thus Bil-Opera mg pressure a e o om O co umn (mm' obtained samples are analyzed by gas chromatography P g) .1.b f .d fb tt f of which result is as follows: X equli rlum vapor pressure o resl ue o o om o column at the operating temperature. Weight percent Xp=rnolar concentration of light components 1n reflux fluid (mol fraction), XDI Impmtym Xf--rnolar concentration of light components in crude composition of the mixture of aask 99. s 0. 2 organic polyisocyanate (mol fraction) Composltionofthemlxtureatthetop ofcolumn. 60.0 40.0 Yf=mo1ar concentration of light components contained in equilibrium vapor of crude organic polyisocyanate in EXAMPLE D feed tray at the operatlng temperature (mol fraction), A purification of crude XDI containing 2 parts of irn- F=feed rate of crude organic polyisocyanate (mol./hr.), purity (I) is carried out by the use of the same apparatus Wztransfer rate of residue (mol./hr.), as in Example C under the following conditions. Xwzmolar concentration of light components in residue The result is as follows: (mol fraction). v

RESULT Composition of the mixture Feed Pressure Temperature C.)

rate at the Top of of top of Bottom Partial Total Flask column solvent column of concon- Solvent (mole) (mm. Hg) column denser denser CBI l XDI CBI l XDI Benzene 0. 98 25 163 10 -20 0. 3 99. 7 30. 2 69. 8 Toluene 0. 68 20 165 30 -20 0. 2 99. 8 32. 5 67. 5 Ethylbenzene 1. 2s 30 164 55 -20 0.3 99.3 33.0 67.0 Chiombenzene 0.68 20 165 45 -20 0.3 99. 7 31.0 69.0 1,2-dichlorobenzene 0. 73 2U 163 10 -20 0. 2 99. 8 31. 6 68. 4 Dichlorcmethane. 0. 62 20 165 0 -20 0. 3 99. 7 31. 7 6s. 3 l-chloro-n-butane. 0. 65 20 163 15 -20 0. 2 99. 8 35. 6 64. 4 Lemmon-penuria- 0. 63 20 165 2o -20 0. 2 99. s 37.1 62. 9 1ch1oronhexane 0. 96 25 165 50 -20 0. 2 99. 8 36. 5 63. 5 Chloroform 0. 63 20 165 10 -20 0. 3 99. 7 31. 3 68. 7 Carbon tetrachloride- 1 31 30 163 10 -20 0. 3 99. 7 30. 6 69. 4 n-Pentane 1. 42 30 165 0 -20 0. 3 99. 7 31. 1 es. 9 n-Hexane.. 1.30 164 0 -20 0. 2 99. s 42. 1 57. 9 n-Heptane 1. 01 25 164 15 -20 0. 3 99. 7 33. 6 66. 4 n-Octane 1. 33 30 162 45 -20 0. 3 99. 7 31. 1 6s. 9 Ligroin. 0.71 25 164 40 -20 0.2 99.8 44.2 65. s Cyclonexane 0. s2 20 164 10 -20 0.2 99.8 40.0 60.0 Cylopentane 0.82 23 165 25 -20 0.3 99.7 31.3 68. 7 Cyclooetane 0. 52 15 163 50 -20 0. 3 99. 7 30. 9 66. 1 Methylcyclohexane. 0. (i5 20 164 15 -20 0. 3 99. 7 36. 3 93. 7

l CBI= Chloromethylbenzylsoeyanate (referred to as impurity (1)).

What is claimed is:

1. A process for the purification by fractionation of a polyisocyanate selected from the group consisting of meta, para and ortho xylylenediisocyanate and mixtures thereof, 4,4-diphenyl-methanediisocyanate, 2,4 and 2,6 tolylenediisocyanate and mixtures thereof and toluene-2,4,6-triisocyanate, lsaid polyisocyanates having been prepared by phosgenation of the corresponding polyamine, which comprises bringing the crude polyisocyanate into contact with a separately introduced chemically inert gas in a lfractionation column, said inert gas being introduced at a rate suicient that the pressure drop in said column is reduced in an amount sufficient to reduce degradation of said polyisocyanate, while maintaining pressure at the top of the column between 5 to 200 mm. Hg, and temperature at the bottom of the column, depending on the polyisocyanate employed between 90 and 220 C. and recovering purified polyisocyanates.

2. A method according to claim 1 wherein the feed rate (C) of inert gas is determined by the formula:

wherein the value of PXEv/PB ranges from 0.05 to 0.50, the value of EV ranges from y0.3 to 1.0 and the value of g3 ranges from 0.2 to 20, and

XD- Yi) X11-Xt R n l* XD- Yf) Xp-Xf (Il) g6=parameter determined by properties of a crude o1'- ganic polyisocyanate and construction of the fractionation apparatus, and

Ev=vaporisation eciency 3. A process according to claim 1 wherein the polyisocyanate is xylylenediisocyanate and the feed rate of inert gas relative to feed rate of crude xylylenediisocyanate is -from 0.2 to 3.0 'by weight, the temperature at the bottom o1" the column being between 100 and 170 C. and the pressure at the top being between 10 and 150 mm. Hg.

4. A process according to claim 1 wherein the inert gas is introduced into the column at a point below the point at which the polyisocyanate is introduced.

5` A method as in claim 1, wherein the inert gas is nitrogen gas.

6. A method as in claim 1, wherein the inert gas is propane gas.

7. A method as in claim 1, wherein the inert gas is carbon dioxide.

8. A process for the purification by fractionation Vof crude xylylenediisocyanate produced by phosgenaton of the corresponding amine which comprises contacting crude or the meta, para or xylylenediisocyanate mixtures thereof with a separately introduced, chemically inert, superheated vapor of an organic solvent having a boiling point of -20 to 150 C. at a pressure of 200 mm. Hg, in a fractionation column, said superheated vapors being introduced at a rate suiicient that the pressure drop in said column is reduced in an amount suflicient to reduce degration of said xylylenediisocyanate, while maintaining pressure at the top of said column at 5 to 200 mm. Hg and temperature at the bottom of said column not higher than 170 C. and recovering purified xylylenediisocyanate.

9. A process according to claim 8 wherein the superheated solvent vapor is introduced into said column at a point below the point at which Xylylenediisocyanate is introduced.

10. A method according to claim 8 wherein the organic solvent is selected from the class consisting of aliphatic hydrocarbons having 2 to 11 carbon atoms, alicyclie hydrocarbons having 5 to 8 carbon atoms, aromatic hydrocarbons, halogenated aliphatic hydrocarbons having 1 to 6 carbon atoms and halogenated benzenes.

11. A method according to claim 8 wherein the crude Xylylenediisocyanate is subjected to an initial distillation to remove high-boilers prior `to contacting with the organic solvent.

12. A method according to claim 8 wherein the organic solvent has a :boiling point of 30 C. to 80 C. at a pressure of 200 mm. Hg.

13. A method as in claim 8 whereinthe organic solvent is cyclohexane.

14. A method as in claim 8 wherein the organic solvent is toluene. l. 15. A method as in claim 8 wherein the organic solvent is ligroin.

References Cited UNITED STATES PATENTS 2,731,081 1/1956 Mayner 203-49 2,884,359 4/ 1959 Bloom 203--70 3,179,680 4/1965 Kober 260--453 (A) 3,210,395 10/1965 McDougall 260-453 (A) 3,211,631 1'0/ 19165 Fuchs 260-45 3 (A) 3,317,606 5/1967 Luberoif et al. 260453(A) 3,405,040 10/1968 Ewald 260-453 (A) 3,410,888 11/1968 Hammond 260-453(A) 3,440,270 4/1969 McMaster et a1. y260-453(A) WILBUR L. BASCOMB, JR., Primary Examiner U.S. Cl. X.R. 

